KR102484034B1 - Polycyclic compound and organic light emitting device comprising same - Google Patents

Abstract

The present specification provides a compound of Formula 1 and an organic light emitting device including the same.

Description

Compound and an organic light emitting device including the same {POLYCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME}

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2020-0007455 filed with the Korean Intellectual Property Office on January 20, 2020, the entire contents of which are incorporated herein.

The present specification relates to a compound and an organic light emitting device including the same.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair, and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as needed.

Most of the materials used in organic light emitting devices are pure organic materials or complex compounds in which organic materials and metals are complexed. can be distinguished. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state when oxidized is mainly used. On the other hand, as an electron injection material or electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state upon reduction is mainly used. As the material of the light emitting layer, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states is preferable, and excitons generated by recombination of holes and electrons in the light emitting layer are formed. A material with high luminous efficiency that converts it into light when it is damaged is preferred.

In order to improve the performance, lifespan or efficiency of an organic light emitting device, the development of organic thin film materials is continuously required.

Korean Patent Publication No. 2016-132822

The present specification provides a compound and an organic light emitting device including the same.

An exemplary embodiment of the present specification provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group,

Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group, at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group,

Ar2 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 5, b is an integer from 0 to 6,

When a is 2 or more, 2 or more R1s are the same as or different from each other,

When b is 2 or more, 2 or more R2s are the same as or different from each other,

* is combined with Formula 2,

[Formula 2]

In Formula 2,

X is O, S, NR, or CR'R";

R, R', R" and R3 are the same as or different from each other, and each independently represents hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;

c is an integer from 0 to 4;

When c is 2 or more, 2 or more R3 are the same as or different from each other,

* is a position bonded to Formula 1 above.

Another exemplary embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

The compounds described in this specification can be used as a material for an organic material layer of an organic light emitting device. When the compound according to an exemplary embodiment of the present invention is applied to an organic light emitting device, hole injection characteristics and electron injection and movement of the device are improved, thereby providing an organic light emitting device having excellent luminous efficiency, low driving voltage, high efficiency and long lifespan. You can get it. Specifically, since the compound described herein has an aryl (Ar1, Ar1') bonded to carbon 2 of anthracene, it has a high HOMO (highest occupied molecular orbital) level to improve hole injection characteristics in the device, and anthracene Since a substituent with excellent electron movement is bonded to the 9th or 10th carbon position of , electron injection and transport in the device can be improved.

1 and 2 illustrate an organic light emitting device according to an exemplary embodiment of the present specification.

Hereinafter, the present specification will be described in more detail.

The present specification provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group,

Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group, at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group,

Ar2 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 5, b is an integer from 0 to 6,

When a is 2 or more, 2 or more R1s are the same as or different from each other,

When b is 2 or more, 2 or more R2s are the same as or different from each other,

* is combined with Formula 2,

[Formula 2]

In Formula 2,

X is O, S, NR, or CR'R";

R, R', R" and R3 are the same as or different from each other, and each independently represents hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;

c is an integer from 0 to 4;

When c is 2 or more, 2 or more R3 are the same as or different from each other,

* is a position bonded to Formula 1 above.

In the compound represented by Chemical Formula 1, a substituted or unsubstituted aryl group is included at the position of carbon 2 of anthracene, thereby increasing the HOMO energy level and improving hole injection. In addition, since Chemical Formula 1 includes a substituent in which Chemical Formula 2 is condensed with dibenzofuran at carbon number 9 or 10 of anthracene, electron transfer is facilitated, and thus electron injection is improved. Therefore, when applied as a host of an organic light emitting device, both hole injection and electron injection effects are improved.

In the present specification, positions 2, 9, and 10 of anthracene are as follows.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, the position where the substituent is substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; Cyano group (-CN); nitro group; hydroxy group; carbonyl group; ester group; imide group; amine group; silyl group; boron group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

As used herein, the term "substituted or unsubstituted" refers to deuterium; an alkyl group; And it means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of aryl groups.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, etc., but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited thereto. .

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc., but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 0 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, etc., but are not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which N of the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and a heteroaryl group.

In the present specification, the alkyl group of the alkylamine group, the N-arylalkylamine group, and the N-alkylheteroarylamine group is the same as the above-mentioned alkyl group.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from examples of heteroaryl groups described later.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as those of the heteroaryl group described later.

In the present specification, the silyl group may be an alkylsilyl group or an arylsilyl group, and further may be a trialkylsilyl group or a triarylsilyl group. The number of carbon atoms of the silyl group is not particularly limited, but is preferably 1 to 30, the number of carbon atoms of the alkylsilyl group is 1 to 30, and the number of carbon atoms of the arylsilyl group is 5 to 30. Specifically, there are trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc., but is not limited thereto. .

In the present specification, the boron group may be -BR ₁₀₀ R ₁₀₁ , wherein R ₁₀₀ and R ₁₀₁ are the same or different, and each independently hydrogen; heavy hydrogen; halogen; nitrile group; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, for example, 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is 10-60 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, phenalenyl group, perylenyl group, chrysenyl group, fluorenyl group, fluoranthenyl group, etc. , but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may bond to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

and

etc. However, it is not limited thereto.

The description of the aryl group described above can be cited except that the arylene group is divalent.

In the present specification, the heterocyclic group includes one or more non-carbon atoms and heterogeneous elements, and specifically, the heterocyclic elements may include one or more atoms selected from the group consisting of O, N, S, and P. . The number of carbon atoms is not particularly limited, but preferably has 1 to 60 carbon atoms, and preferably 2 to 60 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may be an aromatic ring, an aliphatic ring, or a condensed ring thereof. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, Triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, phenanth A phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

The heteroaryl group means a monovalent aromatic heterocyclic group, and the heteroarylene group means a divalent aromatic heterocyclic group. The description of the above heterocyclic group can be cited except that the heteroaryl group and the heteroarylene group are aromatic.

In this specification, "energy level" means the magnitude of energy. Therefore, even when an energy level is displayed in a negative (-) direction from a vacuum level, the energy level is interpreted as meaning an absolute value of the corresponding energy value. For example, the highest occupied molecular orbital (HOMO) energy level means the distance from the vacuum level to the highest occupied molecular orbital. In addition, the lowest unoccupied molecular orbital (LUMO) energy level means the distance from the vacuum level to the lowest unoccupied molecular orbital.

According to an exemplary embodiment of the present specification, * in Formula 1 is combined with Formula 2 below. Specifically, two * in Formula 1 is bonded to two * in Formula 2 below, and the bonding direction is not limited.

[Formula 2]

In Formula 2,

X is O, S, NR, or CR'R";

R, R', R" and R3 are the same as or different from each other, and each independently represents hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;

c is an integer from 0 to 4;

When c is 2 or more, 2 or more R3 are the same as or different from each other,

* is a position bonded to Formula 1 above.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

The definitions of L1, L2, R1 to R3, Ar1, Ar1', Ar2, X and a to c are the same as in Formulas 1 and 2.

In one embodiment of the present specification, Formula 1 is represented by any one of Formulas 2-1 to 2-8 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

In Formulas 2-1 to 2-8,

The definitions of L1, L2, R1 to R3, Ar1, Ar1', Ar2, X and a to c are the same as in Formulas 1 and 2.

In one embodiment of the present specification, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an aryl group having 6 to 60 carbon atoms substituted or unsubstituted with deuterium, and at least one of Ar1 and Ar1' is an aryl group having 6 to 60 carbon atoms substituted or unsubstituted with deuterium.

In another exemplary embodiment, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In another exemplary embodiment, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with deuterium, and at least one of Ar1 and Ar1' is an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with deuterium.

In another exemplary embodiment, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; or a substituted or unsubstituted naphthyl group, and at least one of Ar1 and Ar1' is a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted naphthyl group.

In another exemplary embodiment, Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with heavy hydrogen; or a naphthyl group unsubstituted or substituted with deuterium, and at least one of Ar1 and Ar1' is a phenyl group unsubstituted or substituted with deuterium; Or a naphthyl group with substituted or unsubstituted deuterium.

According to an exemplary embodiment of the present specification, any one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, one of Ar1 and Ar1' is an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with deuterium, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, one of Ar1 and Ar1' is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, any one of Ar1 and Ar1' is a substituted or unsubstituted phenyl group; or a substituted or unsubstituted naphthyl group, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, any one of Ar1 and Ar1' is a phenyl group unsubstituted or substituted with deuterium; or a naphthyl group unsubstituted or substituted with deuterium, and the other is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is a substituted or unsubstituted aryl group, Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with deuterium, and Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium, and Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted naphthyl group, Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1 is a phenyl group unsubstituted or substituted with deuterium; Or a naphthyl group unsubstituted or substituted with deuterium, Ar1' is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is a substituted or unsubstituted aryl group, Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with deuterium, and Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium, and Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is a substituted or unsubstituted phenyl group; or a substituted or unsubstituted naphthyl group, Ar1 is hydrogen; or deuterium.

According to another exemplary embodiment, Ar1' is a phenyl group unsubstituted or substituted with deuterium; Or a naphthyl group unsubstituted or substituted with deuterium, Ar1 is hydrogen; or deuterium.

According to an exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, Ar2 is an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with deuterium; or a heteroaryl group having 2 to 60 carbon atoms unsubstituted or substituted with heavy hydrogen.

According to another exemplary embodiment, Ar2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar2 is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with heavy hydrogen.

In another exemplary embodiment, Ar2 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuranyl group; A substituted or unsubstituted dibenzothiophenyl group; A substituted or unsubstituted carbazolyl group; Or a substituted or unsubstituted Formula 1-A below.

[Formula 1-A]

In Formula 1-A,

Y is O, S, or NRa;

Ra is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

는 L2에 결합되는 위치를 의미한다.

Means a position coupled to L2.

In another exemplary embodiment, Ar2 is a phenyl group unsubstituted or substituted with deuterium; A biphenyl group unsubstituted or substituted with heavy hydrogen; A naphthyl group unsubstituted or substituted with heavy hydrogen; A fluorenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, an alkyl group and an aryl group; A dibenzofuranyl group unsubstituted or substituted with heavy hydrogen; A dibenzothiophenyl group unsubstituted or substituted with heavy hydrogen; A carbazolyl group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and aryl groups; Or a deuterium-substituted or unsubstituted Formula 1-A.

[Formula 1-A]

In Formula 1-A,

Y is O, S, or NRa;

Ra is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

는 L2에 결합되는 위치를 의미한다.

Means a position coupled to L2.

In one embodiment of the present specification, "substituted or unsubstituted" in the substituent definition of Formula 1-A is deuterium; an alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 30 carbon atoms; And it means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ra is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to another exemplary embodiment, Ra is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ra is a substituted or unsubstituted phenyl group.

According to an exemplary embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or an arylene group having 6 to 60 carbon atoms unsubstituted or substituted with heavy hydrogen.

According to an exemplary embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or an arylene group having 6 to 30 carbon atoms unsubstituted or substituted with heavy hydrogen.

According to another exemplary embodiment, the L1 and L2 are the same as or different from each other, and are each independently directly bonded; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and are each independently directly bonded; A phenylene group unsubstituted or substituted with heavy hydrogen; Or a naphthylene group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 30 carbon atoms unsubstituted or substituted with heavy hydrogen; Or an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with heavy hydrogen.

According to another exemplary embodiment, R1 and R2 are the same as or different from each other, and each independently represent hydrogen or deuterium.

According to an exemplary embodiment of the present specification, a is an integer from 0 to 5, and when a is 2 or more, two or more R1s are the same as or different from each other.

According to an exemplary embodiment of the present specification, b is an integer from 0 to 6, and when b is 2 or more, two or more R2s are the same as or different from each other.

In one embodiment of the present specification, X in Formula 2 is O, S, NR, or CR'R".

According to another exemplary embodiment, the X is O.

According to another exemplary embodiment, the X is S.

According to another exemplary embodiment, the X is NR.

According to another exemplary embodiment, the X is CR'R".

According to an exemplary embodiment of the present specification, R, R', R" and R3 in Formula 2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted Or an unsubstituted aryl group having 6 to 60 carbon atoms.

According to another exemplary embodiment, R, R', R" and R3 are the same as or different from each other, and are each independently hydrogen; deuterium; an alkyl group having 1 to 30 carbon atoms unsubstituted or substituted with deuterium; or deuterium. It is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another exemplary embodiment, R is a substituted or unsubstituted phenyl group.

In another exemplary embodiment, R is a phenyl group.

According to an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. to be.

According to another exemplary embodiment, R' and R" are the same as or different from each other, and each independently represents a methyl group or a phenyl group.

In another exemplary embodiment, each of R' and R" is a methyl group.

According to another exemplary embodiment, each of R' and R" is a phenyl group.

In one embodiment of the present specification, R3 is hydrogen or deuterium.

According to an exemplary embodiment of the present specification, c in Formula 2 is an integer from 0 to 4, and when c is 2 or more, two or more R3s are the same as or different from each other.

According to an exemplary embodiment of the present specification, the compound includes one or more deuterium. When the compound contains deuterium, the efficiency and lifetime of the device are improved. Specifically, when hydrogen is replaced with deuterium, the chemical properties of the compound are hardly changed, but the physical properties of the deuterated compound are changed and the vibrational energy level is lowered. Therefore, a compound substituted with deuterium can prevent a decrease in quantum efficiency due to a decrease in intermolecular van der Waals force or a collision due to intermolecular vibration. Also, C-D bonds in a compound can improve the stability of the compound.

According to an exemplary embodiment of the present specification, in the compound of Formula 1, one or more deuterium atoms are bonded to Ar2.

According to an exemplary embodiment of the present specification, in the compound represented by Chemical Formula 1, at least one deuterium is bonded to an aryl substituent among anthracene, Ar2, Ar1, and Ar1'.

According to an exemplary embodiment of the present specification, in the compound of Formula 1, at least one deuterium is bonded to an aryl substituent among anthracene, Ar2, dibenzofuran condensed with Formula 2, Ar1 and Ar1'.

In one embodiment of the present specification, the deuterium substitution rate of the compound is 10% to 100%.

According to another exemplary embodiment, the deuterium substitution rate of the compound is 10% to 99%.

In the present specification, the deuterium substitution rate means the substitution rate of deuterium in a molecule, and can be confirmed through a known method. For example, the substitution distribution of deuterium in a molecule is determined according to the following method. The following TLC-MS is a method for controlling the substitution ratio of deuterium during the synthesis of a compound.

1. Utilizing TLC-MS (Thin-Layer Chromatography/Mass Spectrometry) (method for confirming the synthesis process)

The substitution rate can be calculated based on the maximum value (max. value) of the distribution of molecular weights at the end of the reaction.

In one embodiment of the present specification, Formula 1 is selected from the following compounds.

An exemplary embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1. .

The organic light emitting device of the present specification may be manufactured by conventional organic light emitting device manufacturing methods and materials, except for forming one or more organic material layers using the above compounds.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention includes a hole injection layer, a hole transport layer, a hole transport and hole injection layer, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer, and a layer simultaneously transporting and injecting electrons. It may have a structure including the like. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic material layers.

In one embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or hole transport layer includes the compound.

In one embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or electron injection layer includes the compound.

In one embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound as a host of the light emitting layer.

In one embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes the above compound as a host of the light emitting layer and may further include a dopant.

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode.

According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

The structure of the organic light emitting device of the present invention may have a structure shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In this structure, the compound may be included in the light emitting layer (3).

2 shows an organic light emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 are sequentially stacked on a substrate 1. structure is illustrated. In this structure, the compound may be included in the hole injection layer 5, the hole transport layer 6, the light emitting layer 7 or the electron transport layer 8.

For example, the organic light emitting device of the present specification uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof on a substrate. Depositing to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron suppression layer, an electron transport layer, and an electron injection layer thereon, and then depositing a material that can be used as a cathode thereon. can In addition to this method, an organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a layer for simultaneously transporting and injecting electrons, an electron suppressing layer, a light emitting layer, an electron transporting layer, an electron injection layer, a layer for simultaneously transporting and injecting electrons, and the like. However, it is not limited thereto and may have a single layer structure. In addition, the organic material layer can be formed by a solvent process other than a deposition method using various polymer materials, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or a thermal transfer method. Can be made in layers.

The anode is an electrode for injecting holes, and a material having a high work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode is an electrode for injecting electrons, and it is preferable that the cathode material is a material having a small work function so as to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that serves to facilitate the injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can well inject holes from the anode at a low voltage, HOMO (highest occupied molecular orbital) is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer may play a role of facilitating hole transport. As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer, and a material having high hole mobility is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron suppression layer, the above compounds or materials known in the art may be used.

The light emitting layer may emit red, green or blue light and may be made of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene; Rubrene and the like, but are not limited thereto.

In one embodiment of the present specification, the light emitting layer may include the compound as a host and may include an additional host in addition to the compound.

The additional host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

As the light-emitting dopant, PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonateiridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium), PtOEP (octaethylporphyrin platinum) A phosphorescent material such as or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the light emitting layer emits green light, a phosphorescent material such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as the light emitting dopant. However, it is not limited thereto. When the light emitting layer emits blue light, as the light emitting dopant, a phosphorescent material such as (4,6-F ₂ ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distryl arylene (DSA ), PFO-based polymers, and fluorescent materials such as PPV-based polymers may be used, but are not limited thereto.

In one embodiment of the present specification, a hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used for the hole blocking layer.

The electron transport layer may serve to facilitate electron transport. As the electron transport material, a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer may serve to smoothly inject electrons. The electron injection material has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , compounds having excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

< synthesis example >

synthesis example 1. Synthesis of Compound 1

synthesis example 1-1. Synthesis of compound 1-a

3-Bromo-2-fluorodibenzo[b,d]furan (80g, 302mmol) and (2-chloro-6-hydroxyphenyl)boronic acid (52.0g, 302mml) were added to tetrahydrofuran (THF, 1500ml) After dissolving in, Pd(PPh ₃ ) ₄ (6.97g, 6.0 mmol) and 300ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 1-a (63g, yield 67%).

synthesis example 1-2. Synthesis of compound 1-b

After dissolving compound 1-a (63g, 201mmol) in dimethylformamide (DMF, 1000ml), K ₂ CO ₃ (83.5g, 604mmol) was added, followed by reflux stirring for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to produce a solid. After filtering the solid, it was dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 1-b (46g, 78%).

synthesis example 1-3. Synthesis of compound 1-c

Compound 1-b (46g, 157mmol), bis(pinacolato)diboron (48g, 189mmol), and potassium acetate (KOAc) (31g, 314mmol) were put in a flask with 400ml of dioxane and dispersed. Bis(dibenzylideneacetone)palladium(0) (Pd(dba) ₂ ) (1.81 g, 3.1 mmol) and tricyclohexylphosphine (PCy ₃ ) (1.76 g, 6.3 mmol) were added and refluxed for 24 hours. Stirred. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform and extracting with distilled water three times, the organic layer was distilled under reduced pressure to remove chloroform. Purification was performed using column chromatography to obtain compound 1-c. (42 g, yield 70%)

synthesis example 1-4. Synthesis of compound 1-d

After dissolving 9-bromoanthracene (100 g, 389mmol) and phenylboronic acid (47.4g, 389mmol) in Dioxane (2000ml), Pd(PPh ₃ ) ₄ (9.0g, 7.8mmol) and 2M K ₂ CO ₃ aqueous solution 400ml was added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 1-d (79g, yield 80%).

synthesis example 1-5. Synthesis of compound 1-e

After compound 1-d (79g, 311mmol) was dissolved in 1200ml of DMF, N-bromosuccinimide (55.3g, 311mmol) dissolved in 300ml of DMF was slowly added dropwise. After stirring for 2 hours at room temperature, 3000 ml of water was added dropwise. When a solid was formed, it was dissolved in chloroform after filtering and extracted several times with distilled water. Recrystallization from ethyl acetate gave compound 1-e. (63 g, yield 61%)

synthesis example 1-6. Synthesis of Compound 1-f

After dissolving compound 1-e (63 g, 189 mmol) and phenylboronic acid (23 g, 189 mmol) in Dioxane (1000 ml), Pd(PPh ₃ ) ₄ (4.4 g, 3.8 mmol) and 200 ml of 2M K ₂ CO ₃ aqueous solution were added. and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 1-f (45g, yield 72%).

synthesis example 1-7. Synthesis of Compound 1-g

After compound 1-f (45g, 136mmol) was dissolved in DMF 600ml, N-bromosuccinimide (24.2g, 136mmol) dissolved in DMF 100ml was slowly added dropwise. After stirring at room temperature for 2 hours, 1500 ml of water was added dropwise. When a solid was formed, it was dissolved in chloroform after filtering and extracted several times with distilled water. Recrystallization from ethyl acetate gave compound 1-g. (37 g, yield 66%)

synthesis example 1-8. Synthesis of Compound 1

After dissolving compound 1-g (30 g, 73mmol) and compound 1-c (28g, 73mmol) in Dioxane (400ml), bis(tri-tert-butylphosphine)palladium(0) (0.19g, 0.4mmol) and 50 ml of 2M K ₂ CO ₃ aqueous solution was added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from ethyl acetate gave compound 1 (24g, yield 56%). [M+H ⁺ ]= 587.3

synthesis example 2. Synthesis of Compound 2

Synthesis Example 2-1. Synthesis of compound 2-a

Compound 2-a was obtained in the same manner as in Synthesis Example 1-1, except that (5-chloro-2-hydroxyphenyl)boronic acid was used instead of (2-chloro-6-hydroxyphenyl)boronic acid.

Synthesis Example 2-2. Synthesis of compound 2-b

Compound 2-b was obtained in the same synthesis except for using compound 2-a instead of compound 1-a in Synthesis Example 1-2.

Synthesis Example 2-3. Synthesis of compound 2-c

Compound 2-c was obtained in the same synthesis except for using 2-b instead of compound 1-b in Synthesis Example 1-3.

synthesis example 2-4. Synthesis of compound 2-d

Compound 2-d was obtained in the same manner as in Synthesis Example 1-6, except that naphthalen-1-ylboronic acid was used instead of phenylboronic acid.

synthesis example 2-5. Synthesis of compound 2-e

Compound 2-e was obtained in the same synthesis except for using compound 2-d instead of compound 1-f in Synthesis Example 1-7.

synthesis example 2-6. Synthesis of compound 2

Compound 2 was obtained in the same manner as in Synthesis Example 1-8, except that Compound 2-e was used instead of Compound 1-g and Compound 2-c was used instead of Compound 1-c. [M+H ⁺ ]= 637.2

synthesis example 3. Synthesis of Compound 3

Synthesis Example 3-1. Synthesis of compound 3-a

Compound 3-a was obtained in the same manner as in Synthesis Example 1-6, except that (4-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid was used instead of phenylboronic acid.

Synthesis Example 3-2. Synthesis of compound 3-b

Compound 3-b was obtained in the same synthesis except for using compound 3-a instead of compound 1-f in Synthesis Example 1-7.

synthesis example 3-3. Synthesis of compound 3

Compound 3 was obtained by synthesizing in the same manner as in Synthesis Example 1-8, except that Compound 3-b was used instead of Compound 1-g and Compound 2-c was used instead of Compound 1-c. [M+H ⁺ ]= 753.3

synthesis example 4. Synthesis of Compound 4

synthesis example 4-1. Synthesis of compound 4-a

The compound was synthesized in the same manner as in Synthesis Example 1-1, except that 2-bromo-3-fluorodibenzo[b,d]furan was used instead of 3-bromo-2-fluorodibenzo[b,d]furan. 4-a was obtained.

synthesis example 4-2. Synthesis of compound 4-b

Compound 4-b was obtained in the same synthesis except for using compound 4-a instead of compound 1-a in Synthesis Example 1-2.

synthesis example 4-3. Synthesis of compound 4-c

After dissolving compound 4-b (43g, 147mmol) and (4-hydroxyphenyl)boronic acid (20.3g, 147mml) in THF (600ml), Pd(PPh ₃ ) ₄ (3.4g, 3.0 mmol) and 2M 150ml of K ₂ CO ₃ aqueous solution was added thereto and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 4-c (39g, yield 76%).

synthesis example 4-4. Synthesis of compound 4-d

After dissolving compound 4-c in acetonitrile (600ml), K ₂ CO ₃ (46g, 337mmol) and nonafluorobutane-1-sulfonylfluoride (66g, 217mmol) dissolved in 100ml of distilled water were added. After stirring at room temperature for 3 hours, acetonitrile was removed by distillation under reduced pressure, dissolved in chloroform, and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 4-d (51 g, yield 72%).

synthesis example 4-5. Synthesis of compound 4-e

Compound 4-d (51g, 81mmol), bis(pinacolato)diboron (25g, 97mmol), and KOAc (16g, 161mmol) were added to a flask with 200ml of Dioxane and dispersed. After adding Pd(dba) ₂ (0.93 g, 1.6 mmol) and PCy ₃ (0.90 g, 3.2 mmol), the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform and extracting with distilled water three times, the organic layer was distilled under reduced pressure to remove chloroform. Purification was performed using column chromatography to obtain compound 4-e. (25 g, yield 67%)

synthesis example 4-6. Synthesis of compound 4-f

Compound 4-f was obtained in the same manner as in Synthesis Example 1-4, except that naphthalen-1-ylboronic acid was used instead of phenyl boronic acid.

synthesis example 4-7. Synthesis of compound 4-g

Compound 4-g was obtained in the same synthesis except for using compound 4-f in place of compound 1-d in Synthesis Example 1-5.

synthesis example 4-8. Synthesis of compound 4-h

Compound 4-h was synthesized in the same manner as in Synthesis Example 1-6, except that compound 4-g was used instead of compound 1-e and [1,1'-biphenyl]-3-ylboronic acid was used instead of phenylboronic acid. got it

synthesis example 4-9. Synthesis of compound 4-i

Compound 4-i was obtained in the same synthesis except for using compound 4-h instead of compound 1-f in Synthesis Example 1-7.

synthesis example 4-10. Synthesis of compound 4

Compound 4 was obtained in the same manner as in Synthesis Example 1-8, except that Compound 4-i was used instead of Compound 1-g and Compound 4-e was used instead of Compound 1-c. [M+H ⁺ ]= 789.3

synthesis example 5. Synthesis of Compound 5

synthesis example 5-1. Synthesis of compound 5-a

In Synthesis Example 1-1, 2-bromo-3-fluorodibenzo[b,d]furan was used instead of 3-bromo-2-fluorodibenzo[b,d]furan, (2-chloro-6-hydroxy Compound 5-a was obtained through the same synthesis except that (4-chloro-2-hydroxyphenyl)boronic acid was used instead of phenyl)boronic acid.

synthesis example 5-2. Synthesis of compound 5-b

Compound 5-b was obtained in the same synthesis except for using compound 5-a instead of compound 1-a in Synthesis Example 1-2.

synthesis example 5-3. Synthesis of compound 5-c

Compound 5-c was obtained in the same synthesis except for using 5-b instead of compound 1-b in Synthesis Example 1-3.

synthesis example 5-4. Synthesis of compound 5-d

Compound 5-d was obtained in the same manner as in Synthesis Example 1-6, except that 2-naphthalen-2-ylboronic acid was used instead of phenylboronic acid.

synthesis example 5-5. Synthesis of compound 5-e

Compound 5-e was obtained in the same synthesis except for using compound 5-d instead of compound 1-f in Synthesis Example 1-7.

synthesis example 5-6. Synthesis of compound 5

Compound 5 was obtained by synthesizing in the same manner as in Synthesis Example 1-8, except that Compound 5-e was used instead of Compound 1-g and Compound 5-c was used instead of Compound 1-c. [M+H ⁺ ]= 637.2

synthesis example 6. Synthesis of Compound 6

synthesis example 6-1. Synthesis of compound 6-a

After dibenzo[b,d]thiophen-3-ol (100g, 499mmol) was dissolved in DMF (2000ml), N-bromosuccinimide (89g, 499mmol) dissolved in DMF 500ml was slowly added dropwise. After stirring for 2 hours at room temperature, 3000 ml of water was added dropwise. When a solid was formed, it was dissolved in chloroform after filtering and extracted several times with distilled water. After drying the organic layer with anhydrous magnesium sulfate, the solvent was removed by distillation under reduced pressure. Compound 6-a was obtained by purification through column chromatography. (65 g, yield 65%)

synthesis example 6-2. Synthesis of compound 6-b

In Synthesis Example 1-1, compound 6-a was used instead of 3-bromo-2-fluorodibenzo[b,d]furan, (5-chloro-2- Compound 6-b was obtained in the same synthesis except for using hydroxyphenyl)boronic acid.

synthesis example 6-3. Synthesis of compound 6-c

Compound 6-c was obtained in the same synthesis except for using compound 6-b instead of compound 1-a in Synthesis Example 1-2.

synthesis example 6-4. Synthesis of compound 6-d

Compound 6-d was obtained in the same synthesis except for using 6-c instead of compound 1-b in Synthesis Example 1-3.

synthesis example 6-5. Synthesis of compound 6

Compound 6 was obtained in the same manner as in Synthesis Example 1-8, except that Compound 6-d was used instead of Compound 1-c. [M+H ⁺ ]= 603.3

synthesis example 7. Synthesis of Compound 7

synthesis example 7-1. Synthesis of compound 7-a

After dissolving 4-bromo-2-fluoro-1-iodobenzene (100g, 332mmol) and (5-chloro-2-hydroxyphenyl)boronic acid (57.3g, 332mml) in THF (1500ml), Pd (PPh ₃ ) ₄ (7.68 g, 6.6 mmol) and 300 ml of 2M Na ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 7-a (69g, yield 69%).

synthesis example 7-2. Synthesis of compound 7-b

After dissolving compound 7-a (69g, 229mmol) in DMF (1000ml), K ₂ CO ₃ (95g, 686mmol) was added, followed by reflux stirring for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to produce a solid. After filtering the solid, it was dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 7-b (44g, 68%).

synthesis example 7-3. Synthesis of compound 7-c

After dissolving 7-b (44g, 156mmol) and (2-nitrophenyl)boronic acid (26g, 156mml) in THF (800ml), Pd(PPh ₃ ) ₄ (3.61 g, 3.1mmol) and 2M K ₂ CO ₃ 200ml of the aqueous solution was added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 7-c (39g, yield 77%).

synthesis example 7-4. Synthesis of compound 7-d

After dissolving 7-c (39g, 120mmol) and PPh ₃ (79g, 301mmol) in 600ml of o-dichlorobenzene, the mixture was stirred under reflux for 8 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the mixture was dissolved in chloroform and extracted several times with distilled water. The organic layer was taken, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove chloroform. Purification was performed using column chromatography to obtain compound 7-d (21 g, 60%).

synthesis example 7-5. Synthesis of compound 7-e

After dissolving compound 7-d (21g, 72mmol) and iodobenzene (14.7g, 72mml) in 250ml of DMF, CS ₂ CO ₃ (46.9g, 144mmol) and CuI (2.74g, 14mmol) were added thereto. After raising the temperature to 120 ℃ was stirred for 16 hours. After cooling the reaction solution, 1 L of ethyl acetate was added thereto, transferred to a separatory funnel, and extracted once with an aqueous ammonia solution and extracted three times with 1 L of distilled water. The organic layer was collected, treated with anhydrous magnesium sulfate to remove water, and distilled under reduced pressure. Purification was performed using column chromatography to obtain compound 7-e. (15 g, yield 57%)

synthesis example 7-6. Synthesis of compound 7-f

Compound 7-f was obtained in the same synthesis except for using 7-e instead of compound 1-b in Synthesis Example 1-3.

synthesis example 7-7. Synthesis of compound 7

Compound 7 was obtained in the same manner as in Synthesis Example 1-8, except that Compound 5-e was used instead of Compound 1-g and Compound 7-f was used instead of Compound 1-c. [M+H ⁺ ]= 712.3

synthesis example 8. Synthesis of Compound 8

synthesis example 8-1. Synthesis of compound 8-a

After dissolving 2-bromo-4-chloro-1-fluorobenzene (100g, 477mmol) and (2-hydroxyphenyl)boronic acid (66g, 477mml) in THF (1500ml), Pd(PPh ₃ ) ₄ ( 11 g, 9.5 mmol) and 300 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 8-a (72g, yield 68%).

synthesis example 8-2. Synthesis of compound 8-b

After compound 8-a (72g, 323mmol) was dissolved in DMF 1000ml, N-bromosuccinimide (57.6g, 323mmol) dissolved in DMF 100ml was slowly added dropwise. After stirring at room temperature for 2 hours, 2000 ml of water was added dropwise. When a solid was formed, it was dissolved in chloroform after filtering and extracted several times with distilled water. After removing water from the organic layer with anhydrous magnesium sulfate, the solvent was removed by distillation under reduced pressure. Purification was performed by column chromatography to obtain compound 8-b. (65 g, yield 67%)

synthesis example 8-3. Synthesis of compound 8-c

After dissolving compound 8-b (65g, 216mmol) in DMF (1000ml), K ₂ CO ₃ (89g, 647mmol) was added, followed by reflux stirring for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to produce a solid. After filtering the solid, it was dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 8-c (39g, 64%).

synthesis example 8-4. Synthesis of compound 8-d

After dissolving compound 8-c (39g, 138mmol) and (2-(methoxycarbonyl)phenyl)boronic acid (25g, 138mmol) in THF (500ml), Pd(PPh ₃ ) ₄ (3.2 g, 2.7 mmol) and 100 ml of 2M K ₂ CO ₃ aqueous solution, and stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 8-d (30 g, yield 64%).

synthesis example 8-5. Synthesis of compound 8-e

Compound 8-d (30g, 89mmol) was dissolved in 450ml of THF. After lowering the temperature to 0° C. under a nitrogen atmosphere, 89 ml of 3 M CH ₃ MgBr was slowly added dropwise. The temperature was gradually raised to room temperature. After stirring for 1 hour, the temperature was raised and stirred under reflux for 12 hours. After cooling the reaction solution, it was quenched with HCl solution, and THF was distilled off under reduced pressure. Extraction was performed by adding ethyl acetate (EA) and water. EA was removed under reduced pressure distillation and purified using column chromatography to obtain compound 8-e (22g, yield 73%).

synthesis example 8-6. Synthesis of compound 8-f

Compound 8-e (22g, 65mmol) was dispersed in 250ml of acetic acid and 1.1ml of hydrochloric acid and stirred under reflux for 24 hours. After filtering the precipitated solid, it was washed with water. It was dissolved in EA and extracted several times with water. The organic layer was distilled under reduced pressure and purified using column chromatography to obtain compound 8-f (12g, yield 57%).

synthesis example 8-7. Synthesis of compound 8-g

Compound 8-g was obtained in the same synthesis except for using 8-f instead of compound 1-b in Synthesis Example 1-3.

synthesis example 8-8. Synthesis of compound 8

Compound 8 was obtained in the same synthesis except for using compound 8-g instead of compound 1-c in Synthesis Example 1-8. [M+H ⁺ ]= 613.3

synthesis example 9. Synthesis of Compound 9

synthesis example 9-1. Synthesis of compound 9-a

Compound 1-f (20g) and AlCl ₃ (4g) were put in C ₆ D ₆ (400ml) and stirred for 2 hours. After completion of the reaction, D ₂ O (30ml) was added, stirred for 30 minutes, and trimethylamine (2.4ml) was added dropwise. The reaction solution was transferred to a separatory funnel and extracted with water and toluene. The extract was dried with MgSO ₄ and recrystallized with ethyl acetate to obtain compound 9-a. (15 g, yield 75%)

synthesis example 9-2. Synthesis of compound 9-b

Compound 9-b was obtained in the same synthesis except for using compound 9-a instead of compound 1-f in Synthesis Example 1-7.

synthesis example 9-3. Synthesis of compound 9

Compound 9 was obtained in the same synthesis except for using compound 9-b instead of compound 1-g in Synthesis Example 1-8. [M+H ⁺ ]= 604.3

synthesis example 10. Synthesis of Compound 10

Compound 10 was obtained in the same manner as in Synthesis Example 9-1, except that Compound 2 was used instead of Compound 1-f. [M+H ⁺ ]= 665.4

< Experimental example >

Example 1. Manufacturing of organic light emitting device

A glass substrate coated with indium tin oxide (ITO) to a thickness of 150 nm was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using nitrogen plasma, the substrate was transferred to a vacuum evaporator. A hole injection layer was formed by thermally vacuum depositing the HAT-CN compound to a thickness of 5 nm on the prepared ITO transparent electrode. Subsequently, HTL1 was thermally vacuum deposited to a thickness of 100 nm, and HTL2 was thermally vacuum deposited to a thickness of 10 nm to form a hole transport layer. Subsequently, Compound 1 as a host and BD-A (weight ratio: 95:5) as a dopant were simultaneously vacuum deposited to form a light emitting layer having a thickness of 20 nm. Subsequently, an electron transport layer was formed by vacuum depositing ETL to a thickness of 20 nm. Subsequently, LiF was vacuum deposited to a thickness of 0.5 nm to form an electron injection layer. Then, aluminum was deposited to a thickness of 100 nm to form a cathode to manufacture an organic light emitting device.

The structures of the compounds used in the Examples are as follows.

Example 2 to 10 and comparative example 1 to 5

An organic light emitting device was manufactured in the same manner as in Example 1, except that each of the compounds listed in Table 1 was used instead of Compound 1 as a host of the light emitting layer. At this time, the compounds represented by Formula 1 of the present invention among the following structures were prepared through the same process as in Synthesis Examples 1 to 10, respectively.

In the organic light emitting device prepared in Examples 1 to 10 and Comparative Examples 1 to 5, driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² , and initial luminance at a current density of 20 mA/cm ² The time (LT) to reach 95% of the contrast was measured, and the results are shown in Table 1 below.

compound
(emissive layer host) 10 mA/cm ² measured value LT (T95%) Driving voltage (Vop) Luminous Efficiency (Cd/A) Example 1 compound 1 3.65 7.12 152 Example 2 compound 2 3.72 7.15 137 Example 3 compound 3 3.68 7.03 129 Example 4 compound 4 3.62 7.06 142 Example 5 compound 5 3.75 7.10 133 Example 6 compound 6 3.63 7.12 127 Example 7 compound 7 3.60 6.91 161 Example 8 compound 8 3.71 6.98 146 Example 9 compound 9 3.65 7.12 273 Example 10 compound 10 3.72 7.16 287 Comparative Example 1 compound A 3.98 6.54 103 Comparative Example 2 compound B 3.95 6.33 110 Comparative Example 3 compound C 4.01 6.61 95 Comparative Example 4 compound D 4.15 6.62 119 Comparative Example 5 compound E 4.21 6.59 102

Compared to Comparative Examples 1 to 5, Examples 1 to 10 using the compound represented by Formula 1 of the present invention exhibited characteristics of low voltage and high efficiency, and showed excellent lifespan. In addition, from Examples 9 and 10, it can be confirmed that the lifetime of the device using the deuterium-substituted compound is remarkably improved.

In Comparative Examples 1 to 3, Compounds A to C having different bonding positions of Formula 2 were used, and it can be seen that the driving voltage is higher and the efficiency and lifespan are lower than those of Examples 1 to 10. In addition, compounds D and E used in Comparative Examples 4 and 5 correspond to cases in which Ar1 and Ar1' in Formula 1 are hydrogen, and compounds D and E have low HOMOs, so carrier injection is not smooth. It can be confirmed that the driving voltage is high and not advantageous in terms of efficiency and lifespan.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer

Claims (15)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;
L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,
Ar1 and Ar1' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,
Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
a is an integer from 0 to 5, b is an integer from 0 to 6,
When a is 2 or more, 2 or more R1s are the same as or different from each other,
When b is 2 or more, 2 or more R2s are the same as or different from each other,
* is combined with Formula 2 below,
[Formula 2]

In Formula 2,
X is O, S, or NR;
R and R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,
c is an integer from 0 to 4;
When c is 2 or more, 2 or more R3 are the same as or different from each other,
* is a position bonded to Formula 1 above. The compound according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
The definitions of L1, L2, R1 to R3, Ar1, Ar1', Ar2, X and a to c are the same as in Formulas 1 and 2. delete The method according to claim 1, wherein any one of Ar1 and Ar1' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and the other is hydrogen; or a deuterium compound. The method according to claim 1, wherein L1 and L2 are the same as or different from each other, each independently a direct bond; A substituted or unsubstituted phenylene group; Or a compound that is a substituted or unsubstituted naphthylene group. delete The compound according to claim 1, wherein the compound contains at least one deuterium. The compound according to claim 1, wherein the deuterium substitution rate of the compound is 10% to 100%. The compound according to claim 1, wherein Formula 1 is selected from the following compounds:

. a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is according to any one of claims 1, 2, 4, 5, and 7 to 9. An organic light emitting device comprising a compound according to The organic light emitting device of claim 10, wherein the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound. The organic light emitting device of claim 10, wherein the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or electron injection layer includes the compound. The organic light emitting device of claim 10, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound. The organic light emitting device of claim 10, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound as a host of the light emitting layer. The organic light emitting device of claim 14 , wherein the light emitting layer further includes a dopant.

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